50 results about "Hafnium tetrachloride" patented technology

The invention relates to the technical field of hafnium tetrachloride preparation, in particular to a process method for preparing low-niobium-content hafnium tetrachloride based on a hydrogen reduction method, which comprises the following steps: S1, raw material processing, S2, chlorination and impurity removal, S3, purification, S4, refining and S5, material receiving. According to the method, metal impurities in the hafnium-containing raw stone are removed step by step through the working procedures of raw material processing, chlorination and impurity removal, purification, refining and material receiving, high-purity hafnium tetrachloride with the low niobium content is obtained, in the refining working procedure, under the assistance of the supported catalyst, the metal niobium impurities are removed through a hydrogen reduction method, the removal rate is effectively increased, and the production cost is reduced. And moreover, the process flow is simplified, the energy consumption is reduced, and the method meets the environmental protection requirement.

The invention discloses electronic-grade hafnium oxide and a preparation method and application thereof, and relates to the technical field of high-dielectric-constant materials, and the preparation method comprises the following steps: carrying out chlorination reaction on crushed coarse hafnium oxide and graphite powder to prepare coarse hafnium tetrachloride; purifying the crude hafnium tetrachloride by adopting a molten salt purification method and / or a hydrogenation purification method to prepare high-purity hafnium tetrachloride; the method comprises the following steps: introducing high-purity hafnium tetrachloride into a sublimation furnace, introducing oxygen and an AlCl3 gas-phase catalyst into the sublimation furnace, and oxidizing the high-purity hafnium tetrachloride into hafnium oxide particles and chlorine; and dechlorinating the hafnium oxide particles through a fluidized bed to obtain the electronic-grade hafnium oxide. The hafnium oxide prepared by the preparation method not only has electronic-grade ultra-high purity, but also overcomes various defects of synthesis by using hafnium tetrachloride water; and the technological process is simple, the production efficiency is high, and the production cost is low.

The invention provides a method for preparing high-purity hafnium tetrachloride by wet extraction and separation, which comprises the following steps: stirring and leaching hafnium alloy waste serving as a raw material by using HNO3 and HF mixed acid, then adding thioacetamide, adjusting the pH value to 4-5, stirring and filtering; compounding tributyl phosphate, trioctylphosphine oxide and sulfonated kerosene to obtain a composite extracting agent, and stirring and mixing to form a homogeneous organic phase; in a hydrochloric acid medium, controlling the volume ratio of an organic phase to a water phase to be (2.5-3.5): 1, carrying out three-stage counter-current extraction, and standing for phase splitting; the extracted organic phase passes through an adsorption column filled with iminodiacetic acid modified silica gel; and carrying out reverse extraction by using a hydrochloric acid solution, and then carrying out reduced pressure evaporation concentration, cooling crystallization and dehydration to obtain hafnium tetrachloride. According to the method, the zirconium and hafnium separation efficiency in the hafnium tetrachloride preparation process is improved, and the problem that the content of zirconium and hafnium impurities in the product is too high is solved.

The present application provides a molten salt extraction and distillation separation device for zirconium and hafnium tetrachloride, comprising a distillation tower, a reboiler, a reflux tank, a circulation tank, a sublimator, a gas preheater, and a condenser. During installation, the various components are connected in sequence to obtain a complete molten salt extraction and distillation separation device for zirconium and hafnium tetrachloride. The device has a simple structure, is easy to operate, and is convenient to connect, and is suitable for the molten salt extraction and distillation separation of zirconium and hafnium tetrachloride.

The invention provides a synthesis method of tris (dimethylamino) cyclopentadienyl hafnium, which comprises the following steps: reacting hafnium tetrachloride with sodium dimethylamino at a first temperature under the protection of inert gas to form an intermediate; heating and settling, cooling to a second temperature, dropwise adding cyclopentadiene, and filtering, distilling and purifying to obtain a target product. According to the method, high yield and high purity are achieved by optimizing the raw material ratio and controlling the dropwise adding temperature and the use amount of cyclopentadiene. The byproduct sodium chloride is large in particle and easy to filter, the post-treatment process is remarkably simplified, and the process safety, controllability and industrial adaptability are improved.

Disclosed in the present invention are a thin film deposition device and a deposition method, relating to the technical field of semiconductors. The thin film deposition device comprises an ALD main body, a hafnium source filter, and a hafnium source pipe. Two ends of the hafnium source filter are respectively connected to the ALD main body and the hafnium source pipe; the ALD main body has a deposition chamber, and the hafnium source pipe is in communication with the deposition chamber via the hafnium source filter; and the hafnium source pipe is used for introducing hafnium(IV) chloride gas into the deposition chamber, and the hafnium source filter is used for filtering hafnium(IV) chloride particles from the hafnium(IV) chloride gas. The thin film deposition device provided in the present invention can significantly improve the deposition quality of a hafnium(IV) oxide thin film.

The utility model relates to the technical field of purification furnaces, and discloses a purification furnace for hafnium tetrachloride, which comprises an overturning type heating furnace, the overturning type heating furnace is provided with a frame body and a furnace body, a furnace pipe is inserted in the furnace body, a boss is arranged at the upper end of the circumferential side of the furnace pipe, and a pair of electric cylinders is fixedly arranged on the upper side of the frame body. The upper ends of the electric cylinders are fixedly provided with the same foundation plate, the upper side of the foundation plate is provided with a butt joint pipe in a communicating mode, the boss is located between the furnace body and the foundation plate, the lower side of the foundation plate, the circumferential side of the boss and the upper end of the circumferential side of the furnace body are each fixedly provided with a pair of positioning plates, and a pair of locking plates used for being connected with the positioning plates in a clamping mode is arranged below the foundation plate. A driving assembly is arranged on the upper side of the foundation plate and connected and assembled with the locking plate through a transmission structure. Through the liftable foundation plate, the swingable furnace body and the locking structure, the whole furnace pipe maintenance or replacement process is simpler and more convenient, the operation amount and the maintenance difficulty are reduced, and the working efficiency is improved.

The invention discloses a method for synthesizing butyl zirconate and butyl hafnate, and relates to the technical field of material synthesis, and the method comprises the following steps: mixing and stirring: putting a solvent n-heptane into a reaction kettle, putting a certain amount of hafnium tetrachloride (or zirconium tetrachloride) solid into the reaction kettle, putting a certain amount of n-butyl alcohol into the reaction kettle, and stirring for 30-60 minutes; finally, stirring; organic synthesis: introducing ammonia gas in the stirring process in the step S1, and setting the reaction temperature to be 45 DEG C or below and the reaction pressure to be normal pressure; performing solid-liquid separation; organic distillation; compared with the existing process, the preparation method has the advantages that the preparation cost of the product is greatly reduced through an organic synthesis and secondary distillation treatment mode; and secondly, in the preparation process, the generation of pollutants, especially triethylamine hydrochloric acid, is reduced, the generation of hazardous wastes is avoided, only deacidification and ammonium chloride removal treatment are needed, and compared with the existing process, the cost is greatly reduced, and the environmental protection benefit is relatively obvious.

The automatic hafnium tetrachloride packaging equipment comprises a glove box capable of being filled with inert gas, the glove box comprises a transfer cavity and a main cavity, and the transfer cavity is an independent cavity body and is arranged at the feeding end of the main cavity; the transfer cavity sequentially comprises a vacuum cavity and a plurality of cleaning cavities in the length direction of the main cavity, and the tail end cleaning cavity communicates with the main cavity. An independent transfer cavity is arranged, the transfer cavity sequentially comprises a vacuum cavity and a plurality of cleaning cavities in the length direction of a main cavity, and a first air isolating valve, a second air isolating valve and a vacuumizing assembly are arranged, so that a multi-stage material purification buffer area is jointly constructed. A material bottle firstly enters the vacuum cavity after being fed into the transfer cavity through the first conveying piece, and a vacuumizing program is started after the second air isolating valve is closed, so that most of gas and moisture are effectively removed; and then sequentially passing through a plurality of cleaning cavities, repeating a circulating purification process of vacuumizing-inert gas filling in each stage of cavity, and gradually removing oxygen and moisture left on the surface and in the environment.

This invention relates to the field of hafnium carbide technology and discloses a thermal decomposition preparation process for hafnium carbide precursors. The process includes: dissolving hafnium tetrachloride in anhydrous ethanol, adding propylene oxide dropwise for neutralization and acid removal to obtain a neutral ethanol-hafnium precursor solution; adding ethyl acetoacetate methacrylate and heating for coordination to obtain a hafnium coordination monomer solution; adding acrylonitrile and an initiator and heating for polymerization; when the viscosity of the reaction solution increases, injecting a dimethyl sulfoxide hot solution of melamine as a locking liquid; precipitating, separating, and drying to obtain the hafnium carbide precursor; and after oxidative crosslinking treatment, calcining at high temperature under an inert atmosphere to undergo carbothermic reduction to obtain hafnium carbide powder. This invention achieves molecular-level dispersion of precursor components through liquid-phase coordination and in-situ network locking, effectively reducing the reaction temperature and inhibiting grain agglomeration, thus producing high-purity, ultrafine hafnium carbide powder.

The invention relates to a method for preparing (cyclopentadienyl) tris (dimethylamino) hafnium by using nuclear magnetic control, which comprises the following steps: S1, carrying out heating reflux reaction on hafnium tetrachloride, cyclopentadiene and dimethylamine in the presence of n-butyllithium and n-hexane, and after reacting for a certain time, taking supernate to detect a nuclear magnetic hydrogen spectrum; s2, calculating the ratio a of the integral area of the characteristic peak A to the integral area of the characteristic peak B according to the nuclear magnetic hydrogen spectrum, judging whether a is in a target range or not, if a is in the target range, terminating the reaction, separating a liquid phase, distilling and collecting a crude product; and if a value is greater than the maximum value of the target range, adding cyclopentadiene into the reaction system to continue the reaction, and if a value is less than the minimum value of the target range, continuing the reaction until the ratio of the integral area of the characteristic peak A to the integral area of the characteristic peak B in the nuclear magnetic hydrogen spectrum of the reaction supernatant is within the target range, terminating the reaction, separating the liquid phase, distilling and collecting a crude product. The method can effectively improve the safety of the production process, the raw material conversion rate and the product purity.

The invention provides a method for preparing butyl hafnate from hafnium tetrachloride. The method comprises the following steps: (1) under the protection of inert gas, adding n-butyl alcohol and an organic solvent into a reaction kettle, and then adding hafnium tetrachloride to obtain an initial reaction system; (2) adding a hafnium-based organic metal framework catalyst into the initial reaction system, heating to 40-65 DEG C, controlling the reaction pressure to be 0.1-0.3 MPa, and stirring to react for 3-8 hours to obtain esterification reaction liquid; (3) cooling the esterification reaction liquid to 20-30 DEG C, and separating out solid components in the system by pressure filtration to obtain filtrate; and (4) sequentially carrying out atmospheric distillation, vacuum rectification and precision filtration on the filtrate to obtain the butyl hafnate. By using the hafnium-based catalyst, the reaction efficiency and the product purity of preparing the butyl hafnate from hafnium tetrachloride are improved, and side reaction and equipment corrosion are effectively inhibited. The method is mild in process condition and suitable for industrial large-scale production of butyl hafnate.

The application provides a method for preparing butyl hafnate from hafnium tetrachloride. The method comprises the following steps: (1) adding n-butanol and an organic solvent into a reaction kettle under the protection of inert gas, and then adding hafnium tetrachloride to obtain an initial reaction system; (2) adding a hafnium-based organometallic framework catalyst into the initial reaction system, heating to 40-65 DEG C, controlling the reaction pressure to be 0.1-0.3 MPa, and stirring for 3-8 h to obtain an esterification reaction liquid; (3) cooling the esterification reaction liquid to 20-30 DEG C, separating the solid components in the system by pressure filtration to obtain a filtrate; and (4) sequentially performing normal pressure distillation, vacuum rectification and precision filtration on the filtrate to obtain butyl hafnate. By using the hafnium-based catalyst, the reaction efficiency and product purity of butyl hafnate prepared from hafnium tetrachloride are improved, and the side reaction and equipment corrosion are effectively inhibited. The method has mild process conditions and is suitable for industrial large-scale production of butyl hafnate.

The present invention belongs to the field of semiconductors, and in particular to a hafnium oxide film and its preparation method and application. The preparation method of the hafnium oxide film comprises the following steps: hafnium tetrachloride and cyclopentadiene are subjected to coordination reaction under the conditions of an organic solvent and an auxiliary agent, and then cyclopentadiene hafnium trichloride is obtained by seed induced crystallization method; dimethylamine is added for substitution reaction, and then cyclopentadiene tris (dimethylamino) hafnium is obtained by vacuum distillation crystallization; cyclopentadiene tris (dimethylamino) hafnium is introduced into the reaction chamber of PE-MOCVD equipment, and metal organic chemical vapor deposition is carried out with plasma gas at a deposition temperature, so that cyclopentadiene tris (dimethylamino) hafnium precursor generates hafnium oxide film on the substrate surface; the auxiliary agent is a strong base weak acid salt. The preparation method provided by the present invention can obtain a hafnium oxide film with high purity, high yield and high dielectric constant.

The invention provides an atomic layer etching method and device for hafnium oxide and a semiconductor device, and the method comprises the steps: carrying out multiple times of circular processing on a hafnium oxide layer on the top surface of a to-be-etched device in a reaction cavity until the hafnium oxide layer meets a target etching requirement, each circular treatment comprises the following steps: adjusting the temperature of the device to be etched to a target reaction temperature; providing a process gas, the process gas comprising a chlorine-based gas; dissociating the process gas into a plasma comprising ions and chlorine radicals; filtering ions in the plasma to obtain chlorine free radicals, so that the chlorine free radicals react with the top surface of the hafnium oxide layer at the target reaction temperature to generate a hafnium tetrachloride layer; and heating the device to be etched to a target sublimation temperature so as to gasify and discharge the hafnium tetrachloride layer. According to the invention, damage caused by hafnium oxide in etching can be reduced, and relatively high etching uniformity and precision can be realized.

The invention provides a synthesis method of a high-purity hafnium-zirconium metal complex precursor, and belongs to the technical field of high-dielectric-constant materials for super-large-scale integrated circuits. According to the method, hafnium tetrachloride or zirconium tetrachloride is used as a metal source and sequentially reacts with dialkylamine, n-butyllithium and an alkyl magnesium halide Grignard reagent through a one-pot method in a high-purity inert atmosphere, an intermediate does not need to be separated, and a target precursor is obtained after filtration, washing and rectification. The method is simple and convenient in process operation, mild in reaction condition and low in energy consumption; the raw materials are wide in source and low in price, the product yield reaches 82%-88%, and the metal purity is stabilized to be 6N; when the precursor is used for preparing a hafnium oxide / zirconium thin film through atomic layer deposition (ALD), the thickness of the thin film reaches 14.3 nm under 100 cycles, the non-uniformity is smaller than or equal to 0.90%, the requirement of a gate dielectric layer of a super-large-scale integrated circuit for a high-purity and high-efficiency precursor can be met, and the precursor is suitable for industrial amplification production.

The invention belongs to the field of superhigh-temperature ceramic materials, and particularly relates to a hafnium carbide precursor and a preparation method thereof.The preparation method comprises the steps that n-propyl alcohol hafnium and two special modified compounds are mixed in an inert atmosphere, dicumyl peroxide, benzophenone, triethanolamine and divinyl benzene are added for stirring, and the hafnium carbide precursor is obtained; adding tetrahydrofuran, stirring at a constant temperature to form a homogeneous solution, and finally filtering to obtain a precursor; the two modified compounds are vinyl tris (diethylamino) hafnium and acryloyloxy dibenzoyl hafnium complexes respectively, and the preparation method is realized through substitution reaction of hafnium tetrachloride and amine compounds and coordination reaction of n-propanol hafnium, dibenzoylmethane and acryloyl chloride respectively. The obtained hafnium carbide precursor contains a hafnium source, a modified compound, a cross-linking agent and a solvent, through molecular design, the ceramic yield is remarkably increased, the cracking temperature is reduced, the oxidation resistance and sintering density of final ceramic are improved, and the preparation method is suitable for preparing an ultra-high-temperature ceramic material.

The application discloses a device for preparing high-purity hafnium tetrachloride and removing iron, relates to the technical field of hafnium tetrachloride purification, and comprises a mixing treatment device, the mixing treatment device comprises a first outer shell, a stirring device is arranged below the first outer shell, an inert gas filling pipe is arranged on the left side of the stirring device and at the bottom of the first outer shell, a first electromagnetic control valve is arranged on the inert gas filling pipe, a first discharge pipe is arranged on the right side of the stirring device and at the bottom of the first outer shell, a second electromagnetic control valve is arranged on the first discharge pipe, and a first check valve is arranged below the second electromagnetic control valve and on the first discharge pipe. The raw materials are stirred by the stirring device, inert gas is filled upwards from the bottom of the first outer shell through the inert gas filling pipe, air can be better discharged, the inert gas adopts a gas with a relative molecular mass greater than that of air, for example, argon, and air is discharged to the outside through the exhaust valve.

The embodiment of the invention discloses a method for preparing potassium fluohafnate. The method comprises the following steps: S1, reacting hafnium tetrachloride with a fluorine source to obtain hafnium tetrafluoride; the fluorine source is potassium fluoride; and S2, reacting hafnium tetrafluoride with potassium fluoride to obtain potassium hafnium fluoride. According to the method disclosed by the embodiment of the invention, efficient synthesis of K2HfF6 is realized by optimizing reaction conditions and paths, the process flow is simple, the process conditions are easy to control, the product purity is high, no harmful gas escapes, and the method is suitable for industrial amplification and has a good application prospect in the field of industrial preparation of potassium fluohafnate.

This invention discloses a Ru@Zr x Hf y This invention relates to the field of electrocatalysts and its preparation method. The method includes weighing x mmol zirconium tetrachloride, y mmol hafnium tetrachloride, and 1 mmol terephthalic acid, dissolving them in 40–60 mL of DMF to form solution A; adding 3–5 mL of formic acid to solution A to form solution B and then sonicating the solution; subjecting solution B to a hydrothermal reaction to obtain product C; washing and centrifuging product C with a mixed solvent and then drying it under vacuum to obtain powder; dispersing 200 mg of the powder in 30–40 mL of methanol to form solution D; dispersing 0.1–0.3 mmol ruthenium trichloride powder in solution D and stirring to obtain solution E; washing and centrifuging solution E and then drying it under vacuum to obtain a precursor; heating the precursor to 700 °C and holding it for 2–3 h, then cooling it to 300 °C and allowing it to cool naturally to room temperature to obtain Ru@Zr. x Hf y O2 / C electrocatalyst. It solves the problems of high cost of Pt-based catalysts, easy agglomeration and structural damage of traditional Ru-based catalysts, and poor stability due to interference from corrosive ions in seawater electrolysis.

The invention discloses a method for preparing hafnium dioxide by electrolyzing hafnium tetrachloride, in the method, relatively pure hafnium dioxide is prepared by electrolyzing hafnium tetrachloride, the whole process flow is simple, and the electrolysis efficiency is high. The method comprises the following steps: preparing an HfCl4 solution; adjusting the HfCl4 solution to a sedimentation critical state by using NaOH particles; an electrode plate is inserted into the electrolytic cell, and the HfCl4 solution in the settling critical state serves as electrolyte to be injected into the electrolytic cell; carrying out water bath heating on the electrolytic bath to a preset temperature, and keeping the preset temperature unchanged; starting a direct-current power supply of the electrolytic bath, and keeping a constant-current state, so that the electrolyte reacts; carrying out centrifugal separation on the electrolyte after the reaction, and washing and drying precipitates obtained by centrifugal separation; and calcining the dried precipitate to obtain hafnium oxide.

The invention relates to a preparation method of (bis (trimethylsilyl) amino) tris (pyrrolidinyl) hafnium, which comprises the following steps: (1) reacting bis (trimethylsilyl) sodium amide with hafnium tetrachloride to obtain (bis (trimethylsilyl) amino) hafnium trichloride; (2) reacting tetrahydropyrrole with sodium hydride to obtain sodium pyrrolidinyl; and (3) carrying out a reaction on the (bis (trimethylsilyl) amino) hafnium trichloride obtained in the step (1) and the sodium pyrrolidinyl obtained in the step (2) to obtain the (bis (trimethylsilyl) amino) tris (pyrrolidinyl) hafnium. By optimizing the preparation method of (bis (trimethylsilyl) amino) tri (pyrrolidinyl) hafnium in the prior art, the obtained method is short in synthesis path and simple in synthesis operation, the use of n-butyllithium is avoided, the danger is reduced, the reaction convenience is improved, the raw material cost is low, the product yield and purity are high, and the method is suitable for industrial production. The industrial large-scale production is facilitated.

The application discloses a hafnium chloride automatic packaging equipment, which comprises a glove box in which inert gas can be filled, the glove box comprises a transfer cavity and a main cavity, the transfer cavity is an independent cavity body and is arranged at a feeding end of the main cavity; the transfer cavity comprises a vacuum cavity and a plurality of cleaning cavities in sequence along the length direction of the main cavity, and the tail cleaning cavity is communicated with the main cavity. By arranging the independent transfer cavity, the transfer cavity comprises the vacuum cavity and the plurality of cleaning cavities in sequence along the length direction of the main cavity, and is provided with a first air isolation door, a second air isolation door and a vacuumizing assembly, so that a multi-stage material purification buffer zone is jointly constructed. After the material bottle is sent into the transfer cavity through the first conveying element, the material bottle firstly enters the vacuum cavity, the vacuumizing program is started after the second air isolation door is closed, most of the gas and moisture are effectively removed, then the material bottle sequentially passes through the plurality of cleaning cavities, and the circulating purification process of "vacuumizing-inert gas filling" is repeated in each stage cavity, so that the residual oxygen and moisture in the surface and the environment are gradually removed.

The invention belongs to the technical field of chemical engineering, particularly relates to a zirconium and hafnium fine separation device for high-pressure preparative chromatography, and provides the following scheme aiming at the problems that carrier gas only passes through the surface of molten salt during purging, the gas-liquid contact area is insufficient, and hafnium tetrachloride is easily distributed unevenly in the molten salt due to density difference or local accumulation after being added: the zirconium and hafnium fine separation device comprises an operation tank, an upper sealing cover is arranged above the operation tank; a plurality of sliding holes are formed in the upper circumference of the upper sealing cover at equal intervals, and the sliding rod pieces slide in the corresponding sliding holes. According to the high-pressure preparative chromatography zirconium and hafnium fine separation device disclosed by the invention, carrier gas can be uniformly sprayed out from the inside of molten salt, the gas-liquid contact area is greatly increased, deep impurities are effectively removed, meanwhile, the molten salt can be stirred, the distribution uniformity of hafnium tetrachloride is improved, and the quality of the hafnium tetrachloride is improved. The influence on complex formation and impurity volatilization efficiency caused by uneven distribution in the molten salt due to density difference or local accumulation after the hafnium tetrachloride is added into the molten salt is avoided.

The utility model relates to the technical field of hafnium tetrachloride storage, and discloses a hafnium tetrachloride sulfuric acid storage workshop which comprises workshop wallboards, the drying assembly is arranged on the outer wall of the workshop wallboard, and the drying assembly internally comprises a material storage box used for storing materials, a water suction box used for drying and a collecting box used for collecting; the material storage barrel is rotationally connected to the inner wall of the water suction box, the axial position in the water suction box is rotationally connected with a rotating shaft through a motor, the material storage barrel is fixedly connected to the outer wall of the rotating shaft, three material storage grooves which are arranged in a circumferential mode are formed in the material storage barrel, and door plate assemblies used for controlling opening and closing are arranged on the material storage grooves; the door plate assembly internally comprises a rotating plate and a first reset spring. According to the drying device for the storage workshop, through the arrangement of the storage barrel and the second trigger assembly, the drying agent can be automatically added and replaced, the storage workshop can be dried, intervention of workers is not needed, and the drying convenience of the storage workshop is improved.

The application discloses a purification furnace for tetrachlorohafnium, and relates to the technical field of purification furnaces for tetrachlorohafnium, which comprises a shaft rod installed at the bottom end of the inner cavity of a furnace body through bearings, an impurity accumulation preventing paddle is annularly welded to the outer side of the shaft rod, and a second flow guide ring for annularly dispersing and discharging impurities is welded to the middle part of the inner cavity of the furnace body. The purification furnace for tetrachlorohafnium can timely adjust the reaction conditions in the furnace by dynamically adjusting the opening and closing states of the opening and closing plate, has certain influence on the temperature and pressure in the purification furnace, and can maintain the stability and efficiency of the reaction and purification. The cooperation of the paddle and the opening and closing plate can better separate tetrachlorohafnium gas and impurity particles, a series of flow guide structures facilitate rapid discharge of the impurities in the furnace, reduce the cleaning operation difficulty of workers, buffer the impurities with small particles, prevent a large amount of dust from being generated due to large impact force during discharge, improve the working environment, and protect the health of the operators.

The invention provides a preparation method of cyclopentadienyl tris (dimethylamino) hafnium, which comprises the following steps: (1) mixing a hydrocarbon solvent, hafnium tetrachloride and dimethylamine, and adding an alkali metal compound for reaction; and (2) adding cyclopentadiene into the reaction liquid in the step (1), and reacting to obtain the cyclopentadienyl tris (dimethylamino) hafnium, the alkali metal compound is n-butyllithium. The preparation method comprises the following steps: preferentially mixing hafnium tetrachloride and dimethylamine, then dropwise adding n-butyllithium to prepare tetra (dimethylamino) hafnium, and adding cyclopentadiene to obtain the product. According to the method, the synthesis steps of the product are reduced, the reaction time is shortened, and the yield and the purity are improved.

This invention provides a method, apparatus, and semiconductor device for atomic layer etching of hafnium oxide. The method includes performing multiple cycles of etching on the hafnium oxide layer on the top surface of the device to be etched within a reaction chamber until the hafnium oxide layer reaches the target etching requirement. Each cycle includes: adjusting the temperature of the device to be etched to a target reaction temperature; providing a process gas containing a chlorine-based gas; dissociating the process gas into a plasma containing ions and chlorine radicals; filtering the ions in the plasma to obtain chlorine radicals, and reacting the chlorine radicals with the top surface of the hafnium oxide layer at the target reaction temperature to generate a hafnium tetrachloride layer; and heating the device to be etched to a target sublimation temperature to vaporize and discharge the hafnium tetrachloride layer. This invention can reduce the damage to hafnium oxide during etching and achieve higher etching uniformity and precision.

The invention relates to the technical field of zirconium and hafnium separation, in particular to a method for separating zirconium tetrachloride and hafnium tetrachloride. The method for separating zirconium tetrachloride and hafnium tetrachloride comprises the following steps: (a) carrying out first heating treatment on a mixed system containing crude zirconium tetrachloride salt and alkali metal chlorate to obtain a first mixed system; (b) introducing crude zirconium tetrachloride gas into the first mixed system to carry out gas-liquid mass transfer exchange; zirconium tetrachloride gas generated in the gas-liquid mass transfer exchange process is collected; (c) carrying out second heating treatment on the reaction system after the gas-liquid mass transfer exchange is finished; and (d) carrying out third heating treatment on the reaction system subjected to the second heating treatment, and collecting hafnium tetrachloride gas generated in the third heating treatment process. The method for separating zirconium tetrachloride and hafnium tetrachloride is short in separation process, high in separation efficiency, high in product purity, high in operability, low in cost and capable of achieving continuous and large-scale production.

An apparatus includes a body configured to support a substrate, a first coating, conformal on a surface of the body, that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane, and a second coating, on the first coating, having a hardness that greater than or equal to about 8 gigapascals.